Gilsonitic product



I Patented F ch, 3, 1925.

fur-Tao STATES 'PATENTYOFFICE.

CHARLES N. FORREST, or RAHWAY, HAROLD P. HAYDEN, or 'RA -ITAN TOWNSHIP, MrnDLEsEx COUNTY, NEW JERSEY, AND CRIN n. DOUTHETT, F BEAVER FALLS, PENNsYLvANIA, ASSIGNORS To THE BARBER ASPHALT COMPANY, OF PHILADE1?-. PHIA, PENNSYLVANIA, A CORPORATION or wEs vIRCINIA.

eILsONITrC PRODUCT;

No Drawing. Original application filed August 28, 1919, Serial No. 320,514. Divided and this application filed April 3, 1922. Serial No. 549,187.

To all whom it may concern:

Be it known that We, CHARILFB N. FORREST, of Rahway, in the county of Union and State of New Jersey, HAROLD P. HAYDEN, of Bari- 5 tan Township,-in the county of Middlesex and State of New Jersey, and ORIN R.

DOUTHETT, of Beaver Falls, in the county of Beaver and State of Pennsylvania, citizens of the United States, have invented certain new and useful Improvements in Gilsonitic Products, whereof the following is a specification.

Our invention relates to gilsonitic prodnets and their manufacture, and more especially to products and materials obtainable from ilsonite through sulphonation treatment. e have found that there can be obtained from gil'so'nite and gi'sonitic substances certain products which exhibit various useful properties of true sulphonic substances.

This application is a division ofiour application, Serial No. 320,514, 'filed August 28, 1919, entitled ,Gilso nitic products and their manufacture? 4 The various phases of our invention will be specifically described hereinafter in accordance with the best mode of applying them in a 30 to us. v

As a gilsonitic material to be treated, we Ordinarily prefer gilsonite distillate to native gilsonite; itself. We have Obtained a much greater yield of sulphOnic-p-roducts from t e treatment by preparing the distillate sometime in advance and allowin it to age for a" considerable period be ore being treated. Such distillate may be prepared as follows:

Gilsonite as received from the mine is charged into an iron or steel still, fired withgas or oil (or otherwise suitably heated), and connected to a suitable condenser,--such as an iron pipe condenser water-cooled. Any convenient quantity of gilsonite may be charged,-say 600 poundsto several tons. The still being closed and heat applied. gradually, the gilsonite Wlll liquefyand collect the-bottom of the still, and vapor; and gas evolving from it @will fill the top of the still and pass over practical way at present known into the condenser. As the heating progresses, temperature readings should betaken from time to time on the bod vapor in the upper portion of the stil as well as On the body "of liquid beneath it.

. (Excepting as there may be special Occasion to gradually break it up and decompose it chemically,-whence, mainly, the evolution of vapor. The coming oflof vapor from the still begins ata temperature of some 165 F., and continues up to or even beyond coking temperatures.

Up to the point where the vapor temperature approaches some 550 F., the distilla-f tion may be carried out as rapidly as the contents of the still can be niade to absorb heat. At this point, however, somefgexoe thermic orother peculiar action occurs, so that the evolution of vapor in'the still tends to become excessively rapid. Unless, therefore, the previous heating has been especially slow, it is necessary to reduce the application of heating very greatly as this critical point is approached, in order that undistilled liquid may not be carried over into the condenser, and clog it up so as to render it unusable. In practice, it will usually be found convenient to cut down the fire some 100 F., in advance 'of this temperature. Once this critical point is well passed, the 'fire may .be increased and the distillation pushed onas rapidly as desired tov its conclusion. In practice, the heating need not be carried further than a temperature of product collecting in the bottom of the still; While the vapor coming off from the still may all be led into the iron pipe condenser,

as above suggested, andallzof the strictly vaporous portion thereof there condensed and collected as a liquid, a slightly difierent of the vapor is condensable' at relatively some 850"F., measured on the solid coke procedure is pref rable. A minorportion portion of the normally liquid products will be condensed by the cooling effect of the atmosphere upon the pipe (which thus acts as a sort of auxiliary condenser), and will Collect in the trap, whence it can be drawn 01f fromtime to time and added to the liquid products drawn from the condenser itself. The 'trap also affords a measure of protection against the effects of too rap-id heating at the critical temperature above mentioned. I

condenser. A residuum of heavy oil-will preferably be left in the still, as described under (1).

' The gas from the primary distillation contains ammonia, which can besegregated as ammonium sulphate by a sulphuric scrubbing operation. The coke from both distillations also has a nitrogeneous content recoverable by a similar operation in connection With conversion thereof into fuel gas'by incomplete combustion in a by-product gas. producer. The water eliminated from the crude distillate also contains ammonia in solution, which may, if desired be also converted into ammonium sulphate. For these operations for recovery of ammonia may be used the unconsumed portion of the sulphuric reagent employed in the purification .and sulphonation treatments hereinafter described.

Of the distillates thus produced, we generally prefer to treat the intermediate one.

.Prior to sulphonation treatment, however,

The crude distillate thus obtained contains some 2 to 5% water, which may be eliminated by settling it out in a settling tank.

We prefer not. to treat the water-freed primary, crude distillate thus produced directly, in gross, but to separate it into a plurality of different portions by fractiona-' tion or reduction. The following examples (wherein the temperatures given are the vapor temperatures in the still, unless otherwise Tstated) will sufliciently illustrate the most'convenient methods of 'redistillation:

(1) Condense separately the vapors coming fromthe still up'to 475 1 and from 475 F., to 600 F.,ssubsequently drawing off as residuum the oil unvaporized at the latter temperature, or allowing it to remaln and-mix with the nex't,charge of crude (2) Condense separately the vapors up to 475 F.; from 475 F., to'650 F.; and from 650 F., until the temperature of the material inthe bottom *of the still is about 850 F. By'this procedure, ,an amount of coke the crude oil charge will be produced.

In either of these cases, considerable destructive act-ion occurs in the production of the higher fraetions,'especially the last.

(3) Three fractions nearly similar to those described under (2) may be obtained at temperatures some 100 F., lowerthan' those mentioned by carrying out the redistillation as described in-U. S. Patent No. 877,620, granted January 28, 1908, to Wells, blowing'carbon dioxide or other inert permanent gas through .the liquid in the still. In this case, the destructive actionis much less. It is advantageous to pass the gas and vapor coming off through afilter of fullers earth in the dome of" the still, on its way to the we prefer to subject the gilsonitic material to preliminary purifying treatment with a sulphuric reagent, thus removing therefrom organic bases, olefines, and other impurities that might alter or impair the character and utility of the final products. This preliminary sulphuric treatment may be carried out by agitation of the gilsonitic material with about 5% of sulphuric acid of oil of vitriol grade,-i. e., about 66 B.,fo-r about one half hour. It is desirable to repeat the operation (using fresh acid) one or more times.

After this preliminary step, sulphonation treatment may be carried out bysubjecting the purified gilsonitic oil to the action of a sulphonating reagent. The sulphone-ting reagents which we prefer to use rather than air agitation in order to avoid are oil of vitriol, such as mentioned above, and fuming sulphuric acid or oleunn It is desirable toconduct this treatment in a cast iron vessel, using mechanical agitation such contamination with atmospheric moisture as might interfere with the desired reaction. a

We have found that the quality of certain products ultimately obtainable is improved by carrying out' this treatment progressively, with successive portions of re- ,agent, and segregating the reaction products,

different portionsof reagent, rather than in one single operation'e-say four such treatments, each with an amount of reagent equal to of the material treated. Thus for the first treatment, the reagent may be p11 of vitriol alone; for the second, a mixture of sulphonating reagent equal to 80% of the material tr ated and consisting of 50 parts oil of vitri l and 30 parts oleum.

At the I end of each treatment or operation, the charge in the agitator is allowed to i stand an hour or more, when it will be found to have separated into two distinct layers: a top layer of &residual or mother oil, and a bottom layer", of acid sludges .This latter should be drawn off and thus segregated prior to the next treatment of the mother material.

wit then be neutralized, "as with hydroxide solution-(preferably of specific The residual oil-remaining after. the last treatment has with water "alone a strong emulsifying tendency but it may nevertheless bewashed with alcohol diluted with (sa an equal or double amount of water bout any great difiiculty. The oil may sodium gravity greater than 30 B., inorder to lnsure against emulsification troubles). Af-

. ter the excess of caustic has been drawn off,

the resultant alkaline oil may be washed with water (without trouble from excessive emulsification) to remove any remaining excess of alkali. It may also he distilled with in order to improve its color, and,

steam,

even filtered through fullers earth. 1

The organic material dissolved or 'extracted from theresidual oil by the alcohol 7 appears to. be the cause of the emulsifying pro erty of the oil; for when recovered (by distillation of the alcohol), it itself presents this same property. As thus obtained, this extract derivative is an acid substance, brown to black in' color, and with slight odor. I

"It has, in genera'h-the useful properties of sulphonic acids. tions, therefore, its-characteristic radical or radicals constitute a useful agent for many dilierent purposea acting as hydrolyzer or saponifier for oils, fats and other glycerides or fatty'substances when emaft-rue sulphonici subs't 'ployed in the usual manner, and have exceP lent detergent and emulsifying properties. ejhave; no'proof, however, that it is ance or sulphonation In appropriatev combina- /1s sulphonic. For hydrolizing purposes, the

agent in free acid form maybe used while for detergent or emulsifying purposes, the salt form will ordinarily be preferred.

Asto the general properties of these gilsonitic derivative sulphonic materials, it is to be observed that the alkali salts (i. e.,

both ammonium and alkali metal. salts) 1 are water-soluble, as well as the acid; while the alkaline earth and the other metal salts generally are water-insoluble. (These properties, it will be 'seenfspecially adapt these materials to certain modes of use hereinafter described.) .Both the acid and salt forms are soluble in most organic solvents,

Isuch as benzole, alcohol, petroleum naphtha,

or other distillates,-and both salt and acid forms aremore freely soluble, in such solvents than in water. The dissolution of the acid material in water is peculiar (prob-.

ably owin to impurity), in that as .water is gradually added to the material, it"first" gelatinizes and then goes more freely into solution. This. general solubility in organic solvents sharply distinguishes this gilso-nitic .sulphonic agent (derived by extraction from the sulphonation residual oil) from a somewhat sifnilar gilsonitic sulphonic agent, ob tainable from the sulphonation sludge by dilution of the latter with an equal amount of water (with suitable precautions against over-heating) and allowing the dilute sludge .to stand and settle some twelve hours, and then drawing olf and purifying (by neutralization) the next to the bottom layer thus segregated. In practice, it is most convenient'and desirable to handle, pack, and ship an agent of this sort in the form of' a dry, solid, stable salt, rather-than in its more active free acid form. For detergent and em g 'sifying purposes, the sodium salt willordmarily be preferable, on account of its relatively ow cost. Forsaponifying or hydrolyzing purposes, however, gilt is peculiarly advantageous to employ as the commerczial material a saltwith a volatile base, i

and to produce the active, free acid saponifier therefrom by acidulation m1 when it is to be used,'either before or in the actual treatment of the glycerides,'on account of the facility thus afiorded for securing glycerine water free from saponifier, acidulent or other deleterious impurity. For this purpose, the ammonium salt form of the agent is especially suitable. When this is used, the 1glycerine water subsequently ob: tained wi acidulent, (usually sulphuric acid), and ammonium sa t of the acldulent. By addition contain only acid saponifier,

to this g1 cerine water of a suitable base or salt (suc as calciumhydrate or barium carbonate), insoluble salts of the acidulent and the sa nifier will be formed and pre-' cipitated. is willleave in solution in the in reference to the chemical'character and,

mode of use of the reagent. employed in the principal treatment described above, or to the useful properties of products resulting therefrom. As already stated, however, we do'not mean by; this language that our sulphonic products are true sulphonic substances in the sense of having sulphonic radicals,since we are WlthOllt' clear evidence on this point.

Having thus descri claim: 7 I i 1. An extract-derivative of gilsonitic sulphona-tion residual oil; having, in general, the useful properties of true sulphonic subbed our invention, We

stances; and characterized by a radical Whose alkali salts and free acid are soluble in water, but, Whose alkaline earth salts are Water-insoluble.

2. A gilsonitic sulphonation product, having, in general, the useful properties of true sulphonic substances; serviceable as an agent for the hydrolysis of glycerides; detergent; and characterized by a radical whose alkali .salts and free acid are water-soluble, and

also soluble inbrganic solvents generally, but Whose alkaline earth salts are water-in soluble. y

In testimony whereof, we have hereunto signed our names at Maul-er, N. J this 29th day of March, 1922.

CHARLES N. FORRES'I.

HAROLD P. HAYDEN.

ORIN R. DOUTHETT. Witnesses:

D. J, DESMOND, SHERMME'RRIZZE D1; SANTO. 

